ES2362349T3 - MIXED METAL CATALYST THAT INCLUDES A COMBUSTIBLE BINDER. - Google Patents

Abstract

The present invention pertains to a catalyst composition comprising at least one non-noble Group VIII metal component, at least two Group VIB metal components, and at least about 1 wt. % of a combustible binder material selected from combustible binders and precursors thereof, the Group VIII and Group VIB metal components making up at least about 50 wt. % of the catalyst composition, calculated as oxides. The invention also pertains to a process for preparing the catalyst, to its use in hydroprocessing and to its recycling. The catalyst according to the invention has a higher strength than corresponding binder-free catalysts, and are easier to recycle than catalysts containing a non-combustible binder.

Description

Field of the Invention

The invention relates to a catalyst composition as defined in claim 1. Catalysts comprising at least one non-noble metal component of Group VIII and at least two metal components of Group VIB, composing the metal components of Group VIII and Group VIB at least 50% by weight of the catalyst composition, calculated as oxides, are known in the art. US 4,596,785 describes a catalyst composition comprising the disulfides of at least one non-noble Group VIII metal and at least one Group VIB metal. US 4,820,677 describes a catalyst comprising an amorphous sulfide comprising iron as the non-noble metal of Group VIII and a metal selected from molybdenum, tungsten or mixtures thereof as the metal of Group VIB, as well as a polydentate ligand such as ethylenediamine. In both references, the catalyst is prepared by the coprecipitation of water-soluble sources of a non-noble Group VIII metal and two Group VIB metals in the presence of sulphides. The precipitate is isolated, dried, and calcined in an inert atmosphere. The catalysts of these references are binder free or contain an inorganic oxidized binder, such as alumina. US 3,678,124 describes oxidized catalysts to be used in the oxidative dehydrogenation of paraffin hydrocarbons. Catalysts are prepared by co-precipitating water soluble components of Group VIB metals and non-noble Group VIII metals. The catalysts are free of binder or contain an oxidized binder such as alumina. In WO 9903578 the catalysts are prepared by co-precipitating specified amounts of a source of nickel, molybdenum, and tungsten in the absence of sulphides. The catalyst is free of binder or may contain an oxidized binder such as alumina. The unprepublished international patent application PCT / EP00 / 00354 describes the preparation of sulfurized catalyst compositions by coprecipitation of at least one non-noble metallic component of Group VIII and at least two metallic components of Group VIB to form an oxygen stable precipitate, which subsequently it sulphides. The unprepublished international patent application PCT / EP00 / 00355 describes the preparation of a catalyst composition by contacting at least one non-noble metallic component of Group VIII and at least two metallic components of Group VIB in the presence of a protic liquid, where the At least one of the metal components is at least partially in solid state during contact. The catalysts of unprepublished international patent applications PCT / EP00 / 00354 and PCT / EP00 / 00355 are free of binder or may contain an oxidized binder such as alumina. It appears that binder free catalysts containing a Group VIII metal component and at least two Group VIB metal components are often difficult to prepare. More particularly, it is difficult to prepare shaped particles with sufficient strength without the aid of a binder. On the other hand, catalysts containing a binder of a refractory oxide such as alumina or silica encounter problems when the catalyst has to be discarded or recycled. In that case, the first stage is often to separate the metal components from the inorganic binder, for example, by subsequent bleaching with NaOH and H2SO4. However, such a recycling process is time consuming and expensive. In addition, it cannot be prevented that a part of the expensive metals of Group VIB and Group VIII remain on the binder and therefore be lost. Therefore, an object of the present invention is to provide a catalyst as defined in claim 1 that is both easy to prepare and easy to recycle after use. It has now been discovered that the above objective can be accomplished by using a combustible binder or a precursor thereof in the catalyst preparation process. This combustible binder not only gives the catalyst sufficient mechanical strength but can also be easily removed from the catalyst used by a heat treatment. Therefore, a sophisticated separation of the binder of Group VIB and Group VIII metals is no longer required. The present invention therefore relates to a catalyst composition as defined in claim 1. Coincidentally, catalysts containing, for example, carbon as a vehicle are known in the art. JP 1986-22071, patent application open for public inspection JP 1986-101247, patent application open for public inspection JP 1985-58239, and document US 5,576,261, are described in JP 1986-22071. However, none of these references describe a catalyst composition comprising at least one non-noble metal component of Group VIII and at least two metal components of Group VIB, component metal components of Group VIII and Group VIB at least 50% in weight of the catalyst composition. Catalyst Composition of the Invention In accordance with the present invention a catalyst composition according to claim is provided.

1. In accordance with the present invention there is provided a process for preparing a catalyst composition according to claim 10. In accordance with the present invention there is provided a use of the catalyst composition according to claim 17. In accordance with the present The invention provides a process for recycling a catalyst composition according to claim 18. As indicated above, the catalyst composition according to the invention comprises at least one non-noble metal component of Group VIII, at least two metal components. of Group VIB, and at least 1% by weight of a combustible binder material selected from combustible binders and precursors thereof, the metal components of Group VIII and Group VIB comprising at least 90% by weight of the catalyst composition, calculated in the form of oxides. In the context of the present specification, the phrase "metal component" refers to a salt, oxide, sulfide, or any intermediate between oxide and sulfide of the metal in question. As will be apparent to those skilled in the art, the phrase "at least two metal components of Group VIB" is intended to refer to components of at least two metals of Group VIB, for example, the combination of molybdenum and tungsten. The indications Group VIB and Group VIII used in this specification correspond to the Periodic Table of the Elements applied by the Chemical Abstract Service (CAS system). Suitable Group VIB metals include chromium, molybdenum, tungsten, or mixtures thereof, a combination of molybdenum and tungsten being preferred. Suitable non-noble Group VIII metals include iron, cobalt, nickel, or mixtures thereof, preferably cobalt and / or nickel. Preferably, a combination of metal components comprising nickel, molybdenum, and tungsten or nickel, cobalt, molybdenum, and tungsten, or cobalt, molybdenum, and tungsten is employed in the process of the invention. It is preferred that nickel and / or cobalt make up at least 50% by weight of the total non-noble Group VIII metals, more preferably at least 70% by weight, even more preferably at least 90% by weight. It may be especially preferred that the Group VIII non-noble metal consists essentially of nickel and / or cobalt. It is preferred that molybdenum and tungsten make up at least 50% by weight of the total Group VIB metals, more preferably at least 70% by weight, even more preferably at least 90% by weight. It may be especially preferred that the Group VIB metal consists essentially of molybdenum and tungsten. The molar ratio of Group VIB metals to non-noble Group VIII metals in the catalyst of the invention generally ranges from 10: 1-1: 10 and preferably from 3: 1-1: 3. The molar ratio of different VIB Group metals to each other is believed at this time that is not critical. When molybdenum and tungsten are used as Group VIB metals, the mole ratio of molybdenum: tungsten is preferably in the range of 9: 1-1: 19, more preferably 3: 1-1: 9, much more preferably 3: 1 -1: 6. The catalyst composition comprises at least 90% by weight of the total metal components of Group VIB and Group VIII, calculated as oxides based on the total weight of the catalyst composition. The amount of Group VIB metals and non-noble Group VIII metals can be determined by AAS or ICP. The catalyst composition comprises at least 1% by weight of a combustible binder material, calculated as carbon over the total weight of the catalyst composition, generally 4-10% by weight. The amount of combustible binder material, calculated as carbon, is determined as described below in "characterization methods".

Preferably, the catalyst composition comprises less than 10% by weight, more preferably less than 4% by weight, even more preferably less than 1% by weight of non-combustible binder. Even more preferably, the catalyst is essentially free of non-combustible binders. A non-combustible binder is defined as a material that does not convert to gaseous components, such as carbon dioxide, in air at a temperature above 230 ° C. Examples of non-combustible binders include silica, silica-alumina, alumina, titania, titania-alumina, zirconia, cationic clays or anionic clays such as saponite, bentonite, kaolin, sepiolite or hydrotalcite, and mixtures thereof. That the catalyst composition is essentially free of non-combustible binder means that none of said non-combustible binder has been added during catalyst preparation. It does not exclude that said non-combustible binders are present in small amounts as a catalyst contamination. If so desired, the catalyst composition may comprise any additional material such as phosphorus-containing compounds, boron-containing compounds, fluorine-containing compounds, additional transition metals, rare earth metals, or mixtures thereof, but generally not known. prefer this. It is preferred that the catalyst composition according to the invention consists essentially of at least one non-noble metallic component of Group VIII, at least two metallic components of Group VIB, and at least 1% by weight of a combustible binder material. The expression "consists essentially of" is intended to exclude substantial amounts of other components. It does not exclude other components that are present in small quantities such as catalyst contamination.

"A combustible binder material" within the meaning of the present invention means one or more combustible binders or precursors thereof. A combustible binder within the meaning of the present invention means any binder that is inert under hydroprocessing conditions and that becomes gaseous compounds, such as carbon dioxide, in air at a temperature above 230 ° C. "Inerting under hydroprocessing conditions" within the meaning of the present invention means that the combustible binder is inert in a hydrogen atmosphere up to a temperature of at least 200 ° C. "Inerting" in the sense of the present invention means that the fuel binder is not gasified, which can be easily verified by, for example, TGA analysis. The fuel binder preferably comprises carbon as its major component and optionally further comprises, for example, O, H, and / or N. The fuel binder comprises at least 70% by weight of carbon and at least partially carbonized organic polymers, more preferably at least 90% by weight of carbon. Typical examples are powdered carbon, graphite, activated carbon, pyrocarbon, pyrograph, carbon black, soot and at least partially carbonized organic polymers. The precursor of the suitable combustible binder, at least after carbonization as will be analyzed below, preferably comprises carbon as its major component and optionally further comprises, for example, O, H, and / or N. It comprises at least 70% in weight, more preferably at least 90% by weight, at least after carbonization. Suitable fuel binder precursors include organic polymers, such as polyacrylonitriles, bakelite, polyamides, such as nylon, polyurethanes, cellulose and derivatives thereof, hemicellulosic materials, polyfurfuryl alcohol, styrene-divinylbenzene copolymers, phenol resins, furan resins , polyimide resins, polyphenylene resins, phenolic foams, and polyurethane foams. It is appreciated that when a binder precursor is used, at least partial carbonization is generally necessary to return to the inert polymer under hydroprocessing conditions. If, however, a polymer is used which in itself is inert under hydroprocessing conditions, said carbonization step can be omitted. One or more combustible binders and / or one or more fuel binder precursors may be used. Preferably, Group VIB metals and Group VIII non-noble metals are distributed homogeneously within the combustible binder material. As indicated above, the presence of the fuel binders leads to an increased mechanical strength of the final catalyst composition. Generally, the catalyst composition of the invention has a mechanical strength, expressed as the lateral crushing strength, of at least 0.45 kg / mm (1 lbs / mm) and preferably of at least 1.36 kg / mm (3 lbs. / mm) (measured on extruded products with a diameter of 1-2 mm). Preferably, the catalyst composition in its oxidized state, that is, before any sulfurization stage, has a surface area B.E.T. of at least 10 m2 / g, more preferably of at least 50 m2 / g, and much more preferably of at least 80 m2 / g, measured by a B.E.T. The average pore diameter (50% of the pore volume is below said diameter, the other 50% is above it) of the oxidized catalyst composition is preferably 3-25 nm, more preferably 5-15 nm (determined by adsorption of N2). The total pore volume of the oxidation catalyst composition is generally at least 0.05 ml / g, preferably 0.05-5 ml / g, more preferably 0.1-4 ml / g, even more preferably 0 , 1-3 ml / g, and much more preferably 0.1-2 ml / g, determined by nitrogen adsorption. To further increase the mechanical strength, it may be desirable that the oxidized catalyst composition of the invention have low macroporosity. Preferably, less than 30%, more preferably less than 20% of the pore volume of the catalyst composition is in pores with a diameter of more than 100 nm (determined by mercury intrusion, contact angle: 130 °). The catalyst composition can have many different forms. Suitable forms include powders, spheres, cylinders, rings, and symmetric or asymmetric polylobules, for example tri- and quadrulobules. The particles resulting from extrusion, granulation or agglomeration usually have a diameter in the range of 0.2 to 10 mm, and their resistance is also in the range of 0.5 to 20 mm. Generally these particles are preferred. Powders resulting from spray drying generally have an average particle diameter in the range of 1 m-100 m. In its oxidized state, the catalyst according to the invention has an X-ray diffraction pattern that is essentially amorphous with crystallinity peaks at d = 2.53 Å and d = 1.70 Å. The present invention also belongs to the catalyst composition according to the invention where the metal components have partially or completely converted into their sulfides. In that case, it is preferred that the catalyst be essentially free of Group VIII non-noble metal sulphides. The non-noble metals of Group VIII are preferably present as (non-noble metal of Group VIII) and Sx being x / y in the range of 0.5-1.5, as can be determined by, for example, XRD. Molybdenum and tungsten, if present, are preferably present at least partially in the sulphided catalyst in the form of disulfides, as can be determined by, for example, XRD. Chromium, if present, is preferably present at least partially in the form of sulfide (CrS or Cr2S3), as can be determined by, for example, XRD. Catalyst Preparation Process The present invention also pertains to a process for preparing a catalyst composition as defined in claim 10.

For details about the preparation of a catalyst composition comprising at least one non-noble metal component of Group VIII, at least two metal components of Group VIB, the metal components of Group VIII and Group VIB comprising at least 50% in The weight of the catalyst composition, calculated in the form of oxides, refers to WO-0041811A and WO-0041810A. The crucial point of the process according to the invention is that the metal components are reacted in the presence of a protic liquid. Any protic fluid that does not prevent the reaction can be used. Suitable liquids include water, carboxylic acids, lower alcohols such as ethanol and propanol and mixtures thereof. The use of water is preferred. The at least three metal components used in the process according to the invention, namely at least one Group VIII metal component and at least two Group VIB metal components may be in a solute state or at least partially in a solid state during the process of the invention. Thus, the reaction may involve three solute components, two solute components and one at least partially solid component, one solute component and two at least partially solid components, and three at least partially solid components. The reaction involves precipitation and, optionally, depending on the state of the various components, also dissolution and re-precipitation. Generally, there are two possible ways of contacting the metal components with each other, specifically by combining and reacting the metal components in solution to form a precipitate (hereinafter referred to as the "solution path"), or by combining and reacting the metal components in the presence of a protic liquid with at least one of the metal components that remain at least partially in a solid state (hereafter referred to as the "solid path"). This last route may be preferred. In the solution route, the metal components dissolve completely when combined and / or reacted to form a precipitate. It is possible, for example, to combine the metal components when they are already dissolved and then reacted to form a precipitate: However, it is also possible to combine one or more of the metal components that are partially or completely in the solid state with metal components additional. However, in this case, care should be taken that the metal components that are partially or completely in the solid state dissolve when they are present in the reaction mixture. In other words, at least once during the process of the solution route, all metal components must be completely present in the form of a solution. Precipitation can be done by, for example,

(to)

the change of the pH during or after the combination of the metal component solutions to a value such that precipitation is induced;

(b)

the addition of a complexing agent during or after the combination of the metal component solutions, said complexing agent complexing one or more of the metals to prevent precipitation of the metals, and thereafter changing the reaction conditions, such as temperature or pH, so that the complexing agent releases the metals for precipitation;

(C)

temperature adjustment during or after the combination of the metal component solutions to a value such that precipitation is induced;

(d)

the decrease in the amount of solvent during or after the combination of the metal component solutions so that precipitation is induced;

(and)

the addition of a non-solvent during or after the combination of the metal component solutions to induce precipitation thereof, meaning a non-solvent that the precipitate is essentially insoluble in this solvent;

(F)

the addition of an excess of any of the components to such a degree that precipitation is induced. The pH adjustment in, for example, option (a) or (b) can be done by adding a base or an acid to the mixture of

reaction. However, it is also possible to add compounds that after increasing the temperature will decompose into hydroxide ions or H + ions, which will increase and decrease the pH, respectively. Examples of compounds that will decompose after increasing the temperature and therefore increase or decrease the pH are urea, nitrites, ammonium cyanate, ammonium hydroxide, and ammonium carbonate. The solid route comprises combining and reacting the metal components, with at least one of the remaining metal components at least partially in the solid state. More in particular, it comprises adding the metal components to another and simultaneously and / or afterwards causing them to react. Therefore, at least one metallic component is added in the solid path at least partially in the solid state and this metallic component remains at least partially in the solid state during the entire reaction. The expression "at least partially in solid state" in this context means that at least part of the metal component is present in the form of a solid metal component and, optionally, another part of the metal component is present in the form of a solution in the protic liquid. . A typical example of this is a suspension of a metallic component in a protic liquid, where the metal is at least partially present in the form of a solid and, optionally, partially dissolved in the protic liquid. It is possible to first prepare a suspension of a metallic component in the protic liquid and add, simultaneously or successively, additional solution (s) and / or suspension (s) comprising (n) dissolved metal component (s) (s) and / or suspended (s) in the protic fluid. It is also possible to combine solutions simultaneously or successively first and then add additional suspension (s) and optionally solution (s) simultaneously or successively. As long as at least one metal component is at least partially in the solid state during the solid path, the amount of metal components that are at least partially in the solid state is not critical. Therefore, it is possible that all metal components are combined in the solid path to be applied at least partially in the solid state. Alternatively, a metal component that is at least partially in a solid state can be combined with a metal component that is in a solute state. For example, one of the metal components is added at least partially in the solid state and, for example, at least two and preferably two metal components are added in the solute state. In another embodiment, for example, two metal components are added at least partially in the solid state and at least one and preferably a metal component is added in the solute state. That a metal component is added "in a solute state" means that the entire amount of this metal component is added in the form of a solution in the protic liquid. As will be clear from the foregoing, it is possible to add the non-noble metal component of Group VIII and the metal component Group VIB in various ways: at various temperatures and pH, in solution, in suspension, moistened or as such, simultaneously or sequentially It should be appreciated that it is preferred not to use sulfur-containing metal components, since these components and the resulting products are not stable in relation to oxygen, which implies that all the process steps after the addition of this metal component, even those to at a lower temperature, they will have to be applied in an inert atmosphere. Non-noble water soluble Group VIII metal components suitable for use in the process of the invention include salts, such as nitrates, hydrated nitrates, chlorides, hydrated chlorides, sulfates, hydrated sulfates, formates, acetates, or hypophosphite. Suitable water soluble nickel and cobalt components include nitrates, sulfates, acetates, chlorides, formates or mixtures thereof as well as nickel hypophosphite. Suitable water soluble iron components include acetate, chloride, formate, nitrate, iron sulfate or mixtures thereof. Suitable water soluble Group VIB metal components include salts of Group VIB metals such as monomolibdates and ammonium tungstates or alkali metals as well as water-soluble isopoli compounds of molybdenum and tungsten, such as meta-tungstic acid, or soluble heteropoli compounds in molybdenum or tungsten water which additionally comprise, for example, P, Si, Ni, or Co or combinations thereof. Suitable water soluble isopoli and heteropoli compounds are given in Molybdenum Chemicals. Chemical data series, Bulletin Cdb-14, February 1969 and in Molybdenum Chemicals. Chemical data series, Bulletin Cdb-12a-revised, November 1969. Suitable water soluble chromium compounds include chromates, isopolychromates and ammonium and chromium sulfate. If the protic liquid is water, suitable non-noble Group VIII metal components that are at least partially in solid form during the process of the invention comprise non-noble Group VIII metal components with low water solubility such as citrates, oxalates, carbonates, hydroxycarbonates, hydroxides, phosphates, phosphides, aluminates, molybdates, tungstates, oxides, or mixtures thereof. Oxalates, citrates, carbonates, hydroxycarbonates, hydroxides, phosphates, molybdates, tungstates, oxides, or mixtures thereof are preferred, with hydroxycarbonates and carbonates being much more preferred. Generally, the molar ratio between hydroxy groups and carbonate groups in hydroxycarbonates is in the range of 0-4, preferably 0-2, more preferably 0-1, and much more preferably 0.1-0, 8. If the protic liquid is water, suitable Group VIB metal components that are at least partially in solid state during contact comprise Group VIB metal components with low water solubility, such as di- and trioxides, carbides, nitrides, salts of aluminum, acids, or mixtures thereof. Preferred Group VIB metal components that are at least partially in solid state during contact are di- and trioxides, acids, and mixtures thereof. Suitable molybdenum components include molybdenum di- and trioxide, molybdenum sulfide, molybdenum carbide, molybdenum nitride, aluminum molybdate, molybdic acids (for example, H2MoO4), ammonium phosphomolbdate, or mixtures thereof, being preferred molybdic acid and molybdenum di- and trioxide. Suitable tungsten components include tungsten di-y trioxide, tungsten sulfide (WS2 and WS3), tungsten carbide, ortho-tungstic acid (H2WO4 * H2O), tungsten nitride, aluminum tungstate (also meta-or poly-polystate) , ammonium phosphotungstate, or mixtures thereof, with ortho-tungstic acid and tungsten di- and trioxide being preferred. If the protic liquid is water, the solubility of the non-noble metal components of Group VIII and the metal components of Group VIB that are at least partially in the solid state during the process of the invention is generally less than 0.05 mol / (100 ml of water at 18 ° C). As indicated above, the combustible binder material is added before, during and / or after contact of the metal components. If the combustible binder material is added before and / or during the contact of the metal components, it preferably does not prevent the reaction of the metal components. Generally, the addition of the combustible binder material after contact, that is, the combination and reaction, of the metal components is preferred. The combustible binder material may be added before contacting the metal components, for example, by adding it to one or more but not all the metal components or vice versa, and subsequently adding the metal components not yet added simultaneously or successively. The combustible binder material may be added during contact of the metal components, for example, by simultaneously combining the fuel binder material and the metal components or by first combining the metal components simultaneously or successively and then adding the fuel binder material during the reaction of the metal components. combined. The combustible binder material can be added after contact of the metal components, for example, by adding them directly to the reaction mixture obtained after the reaction of the metal components. However, it is also possible to add the combustible binder material after a solid-liquid separation, a washing step or any of the additional process steps that will be analyzed in detail below.

Optional additional process steps are, for example, spray drying, (instant) drying, grinding, kneading, suspension mixing, dry or wet mixing, shaping, calcining and / or sulfurization. Dry mixing means mixing the catalyst composition in the dry state with, for example, the combustible binder material in the dry state. The wet mix, for example, comprises mixing the wet filter cake comprising the catalyst composition and, optionally, for example, the combustible binder material in liquid, powder or dry filter cake form to form a homogeneous paste of the same. The conformation comprises, for example, extrusion, agglomeration, granulation and / or spray drying. The calcination, if any, is generally carried out at a temperature of, for example, 100 ° -600 ° C, preferably 150 ° to 550 ° C, more preferably 150 ° C-450 ° C, for a time ranging from 0.5 to 48 hours. The calcination can be carried out, for example, in an inert atmosphere or in an atmosphere containing oxygen, such as air. A calcination step can be performed before the addition of the combustible binder material to the catalyst composition, and / or after said addition. If a calcination step is performed after the addition of the combustible binder material, care should be taken that the combustible binder material does not decompose during said calcination. This can be done by performing said calcination in the absence of oxygen,

or in an atmosphere containing oxygen at a temperature below 230 ° C. The sulfuration can be carried out, for example, in the gas or liquid phase. It is generally done by contacting the precipitate with a sulfur-containing compound such as elemental sulfur, hydrogen sulfide, DMDS, or polysulfides. Sulfurization can generally be done in situ and / or ex situ. Preferably, the sulfurization is performed ex situ, that is, the sulfurization is carried out in a separate reactor before the sulfurized catalyst composition is loaded into the hydroprocessing unit. In addition, it is preferred that the catalyst composition is sulfur both ex situ and in situ. For additional details regarding these additional process steps, reference is made to document WO-0041811A (heading "catalyst preparation process" in "process stage (ii)" and "optional process stages") and document WO -0041810A (heading "process of the invention" in "(B) subsequent process steps"). "A combustible binder material" within the meaning of the present invention means one or more combustible binders or precursors thereof. If the combustible binder material comprises more than one combustible binder or precursor thereof, each binder or binder precursor may be added at any stage before, during or after contact of the metal components. A binder or binder precursor may be added, for example, before the contact of the metal components and another binder or binder precursor may be added after the contact of the metal components. At least if the fuel binder material consists essentially of a fuel binder precursor, the process generally comprises a stage in which the fuel binder precursor becomes the corresponding fuel binder. Said process step may be, for example, pyrolysis in an inert atmosphere that leads to at least partial carbonization of the binder precursor. Preferably, the inert atmosphere comprises an inert gas, such as nitrogen. More preferably, the inert atmosphere is essentially oxygen free. Said pyrolysis is preferably performed at a temperature of 300 ° -600 ° C and more preferably 350 ° -600 ° C. In principle, higher temperatures can also be applied for the conversion of the fuel binder precursor into the fuel binder. However, in order not to damage the additional constituents of the catalyst, higher temperatures are less preferred. Pyrolysis can be performed in the presence of steam. As will be apparent to those skilled in the art, the temperature ranges for pyrolysis will depend on the type of fuel binder precursor employed and can easily be determined by, for example, thermogravimetric analysis (TGA).

The conversion of the fuel binder precursor into the fuel binder can be carried out in any area of the process of the invention after the addition of the fuel binder precursor. If a mixture of a fuel binder and a fuel binder precursor is used, a pyrolysis is still preferred. If desired, the fuel binder or the fuel binder precursor can be subjected to a reaction with, for example, compounds containing phosphorus or nitrogen to introduce functional groups into the fuel binder (precursor). The combustible binder material can be added, for example, in the form of a liquid or powder. In this case, the catalyst can be prepared, for example, as follows: In a first stage, the metal components are brought into contact and reacted by the solid or solution route. The progress of the reaction can be monitored by XRD, pH change, or any suitable mode used in the art. The catalyst composition is isolated by filtration, after which the filter cake is wet mixed with the combustible binder material. The mixture is formed, for example, by extrusion, and the shaped particles are dried and optionally calcined and / or when appropriate they are subjected to a pyrolysis step. Optionally, the resulting composition is sulphided. The catalyst can also be prepared by successive steps of adding the combustible binder material before or during the contact of the metal components according to the solid or solution route, isolating the catalyst composition by filtration, forming the filter cake, by for example, by extrusion, drying, and optionally calcining, pyrolizing, and / or sulfuring the resulting composition. If the fuel binder material is a fuel binder precursor, the process embodiments will generally comprise a step to convert the fuel binder precursor into the fuel binder, for example, a pyrolysis. Alternatively, you can use a shaped fuel binder material, such as a shaped carbon vehicle. In this case, the metal components are preferably contacted in the presence of the formed combustible binder material. If the metal components are contacted according to the solution route, Group VIB metals and Group VIII non-noble metals will predominantly be located in the pores of the combustible binder material formed in the final catalyst composition. Said shaped fuel binder material preferably has a pore volume of at least 0.5 ml / g, more preferably 0.8-1.5 ml / g, measured by nitrogen adsorption. A combustible binder material formed in the solid pathway can also be used. In this case, for example, the metal component that remains at least partially in the solid state can be co-formed, for example, co-extruded with the combustible binder material, and the resulting shaped material can be contacted with the metal components that are employed in a solute state. Use according to the invention The catalyst composition according to the invention can be used in almost all hydroprocessing processes to treat a plurality of supplies under wide-range reaction conditions, for example, at temperatures in the range of 200 ° to 450 ° C, hydrogen pressures in the range of 5 to 300 bar, and velocities in space (LHSV) in the range of 0.05 to 10 h-1. The term "hydroprocessing" in this context encompasses all processes in which a supply of hydrocarbon is reacted with hydrogen at elevated temperature and high pressure, including hydrogenation, hydrodesulphurization, hydrodesnitrogenation, hydrodemetalization, hydrodearomatization, hydroisomerization, hydrodeparaffination, hydrocracking, and hydrocracking under mild pressure conditions, which is commonly known as mild hydrocracking. The catalyst composition of the invention is particularly suitable for hydrotreating hydrocarbon feedstocks. Such hydrotreatment processes comprise, for example, hydrodesulphurization, hydrodesnitrogenation, and hydrodearomatization of hydrocarbon feedstocks. Suitable raw materials are, for example, intermediate distillates, quero, naphtha, vacuum diesel oils, and heavy diesel oils. Conventional process conditions may be applied, such as temperatures in the range of 250 ° -450 ° C, pressures in the range of 5-250 bar, velocities in the space in the range of 0.1-10 h-1 and proportions H2 / oil in the range of 50-2000 Nl / l. Recycling process of the invention As indicated above, the binder of the catalyst composition of the present invention can be easily removed from the catalyst composition by heat treatment. Accordingly, the present invention also pertains to a process for recycling a used or residual catalyst composition comprising at least one non-noble metallic component of Group VIII, at least two metallic components of Group VIB, and a combustible binder, said process comprising treating thermally used or residual catalyst composition in an atmosphere containing oxygen at a temperature of at least 300 ° C. Preferably, the heat treatment is performed in air. Preferably, the temperature is chosen above 400 ° C, more preferably above 500 ° C, even more preferably above 600 ° C, and much more preferably above 700 ° C, but preferably below 850 ° C. The metal components of Group VIB and the resulting non-noble metal components of Group VIII may be recovered in any conventional manner, as described in Catalysis Today, 30 (1996) 223 (review by E. Furimsky, Spent refinery catalysts: environment, safety and utilization, chapter 4.1.1). It is appreciated that regardless of the method chosen, the recovery process is significantly simplified by the absence of a binder. Characterization Methods

(to)

 Side Crush Resistance (SCS) First, the length of, for example, an extracted particle is measured and then the extruded particle is subjected to compression load (11.34 kg (25 lbs) in 8.6 seconds) by a mobile piston. The force necessary to measure crush the particle. The procedure is repeated with at least 40 extruded particles and the average is calculated as the force (kg (lbs)) per unit length (mm). This method is applied to particles shaped with a length not exceeding 7 mm.

(b)

 Pore volume (adsorption of N2) The pore volume determination by adsorption of N2 was performed as described in the PhD thesis of J.

C.

 P. Broekhoff (University of Technology Delft 1969).

(C)

 Stability of the fuel binder by thermogravimetric analysis (TGA) The samples were heated in a preselected atmosphere at a heating rate of 10 ° C / minute and the change in sample mass over time was recorded. The preselected atmosphere chosen was the composition soda in which the stability of the fuel binder has to be tested. Details can be found Additional about TGA in Appl. Chem., 52-1, 2385-2391 (1980).

(d)

 Carbon content To determine its carbon content, the catalyst composition was subjected to heating in an oven of induction in an oxygen flow. Any carbon contained in the catalyst composition in this way is oxidized in carbon dioxide. Carbon dioxide was analyzed using an infrared cell with a system of detection based on IR characteristics of CO2. The resulting signals were compared with the signals of calibrated standards to obtain the amount of carbon dioxide and therefore the amount of carbon contained in The catalyst composition The present invention is illustrated by the following examples:

Example 1

A mixed metal composition was prepared via the solid route from nickel hydroxycarbonate, MoO3, and H2WO4. The resulting precipitate was filtered and a wet filter cake containing approximately 20% by weight of MoO3, 40% by weight of WO3, and 40% by weight of NiO (determined after calcination at 300 ° C in air) was obtained. ). A fuel binder precursor was prepared from furfuryl alcohol by mixing 200 ml of furfuryl alcohol with 200 ml of water and 1 ml of concentrated sulfuric acid, slowly heating the resulting mixture to 90 ° C, and maintaining it at 90 ° C for 10 minutes. A two phase system was obtained. The organic phase (containing polyfurfuryl alcohol) was separated from the aqueous phase in a separatory funnel, yielding 55.6 g of organic liquid. 500 g of the wet filter cake of the mixed metal composition was mixed in a powder base with the organic liquid. The mixture was then extruded and dried at 120 ° C in air for 2 hours. To convert the fuel binder precursor into a fuel binder, the resulting composition was heated at 300 ° C under nitrogen flow for 2 hours. The catalyst composition had a lateral crush strength (SCS) of 2.54 kg * mm-1 (5.6 lbs * mm-1). The carbon content was 4.83% by weight. It could be confirmed by TGA that the catalyst composition is stable under hydrogen atmosphere (50% by volume of hydrogen in helium) to a temperature of 270 ° C. It could be further confirmed by TGA that the combustible binder can be removed from the catalyst composition by heating in air in a temperature range between 250 ° and 700 ° C.

Example 2

A catalyst composition was prepared as described in Example 1, except that the resulting composition was heated at 420 ° C under nitrogen flow for two hours to convert the fuel binder precursor into a fuel binder. The lateral crush resistance (SCS) was 2.63 kg * mm-1 (5.8 lbs * mm-1). The carbon content of this catalyst composition was 4.4% by weight. It could be confirmed by TGA that the catalyst composition is stable under hydrogen atmosphere (50% by volume of hydrogen in helium) up to a temperature of 370 ° C. It could be further confirmed by TGA that the combustible binder can be removed by heating in air in a temperature range between 350 ° and 700 ° C.

Comparative Example A

A mixed metal composition was prepared as described in Example 1. The resulting wet filter cake was mixed so that a mixture with extrusion capacity was obtained. The mixture was then extruded, dried at 120 ° C, and calcined at 300 ° C in air. The lateral crush resistance (SCS) was 2.09 kg * mm-1 (4.6 lbs * mm-1). This example shows that the lateral crush resistance of the resulting catalyst is greatly reduced if a combustible binder is absent.

Claims (17)

one.

A catalyst composition comprising at least one non-noble metal component of Group VIII, at least two metal components of Group VIB, and at least 1% by weight of a combustible binder material, calculated as carbon over the total weight of the catalyst composition , composing the metal components of Group VIII and Group VIB, calculated in the form of oxides, at least 90% by weight of the catalyst composition, the combustible binder comprising at least 70% by weight of carbon and comprising an organic polymer at less partially carbonized.

2.

A catalyst composition according to claim 1, wherein the combustible binder is converted into gaseous components comprising carbon dioxide if it is in air at a temperature above 230 ° C.

3.

The catalyst composition of any one of the preceding claims consisting essentially of at least one non-noble metal component of Group VIII, at least two metal components of Group VIB, and at least 1% by weight of the combustible binder material.

Four.

The catalyst composition of any one of the preceding claims, wherein the non-noble metal component of Group VIII comprises cobalt, nickel, or iron.

5.

The catalyst composition of claim 4, wherein the nickel and cobalt make up at least 50% by weight of the non-noble metal components of Group VIII, preferably at least 70% by weight, more preferably at least 90% by weight, much more preferably almost all non-noble metal components of Group VIII, calculated as oxides.

6.

The catalyst composition of any one of the preceding claims, wherein the metal component of Group VIB comprises at least two of molybdenum, tungsten, and chromium.

7.

The catalyst composition of claim 6, wherein molybdenum and tungsten make up at least 50% by weight of the Group VIB metal components, preferably at least 70% by weight, more preferably at least 90% by weight , much more preferably substantially all the metal components of Group VIB, calculated as oxides.

8.

The catalyst composition of any one of the preceding claims, wherein the organic polymer is selected from the group consisting of polyacrylonitriles, bakelite, polyamides, polyurethanes, cellulose and derivatives thereof, hemicellulosic materials, polyfurfuryl alcohol, styrene-divinylbenzene copolymers , phenol resins, furan resins, polyimide resins, polyphenylene resins, phenolic foams, and polyurethane foams, and mixtures thereof.

9.

The catalyst composition of any one of the preceding claims, wherein at least part of the metal components is in sulfur form.

10.

A process for preparing a catalyst composition according to any one of the preceding claims, said process comprising contacting at least one metal component of Group VIII with at least two metal components of Group VIB in the presence of a protic liquid, wherein the binder Fuel is added before, during and / or after contact of the metal components.

eleven.

The process of claim 10, wherein the contact of the metal components comprises combining and reacting the metal components to form a precipitate.

12.

The process of claim 10, wherein the contact of the metal components comprises combining and reacting the metal components in the presence of a protic liquid, with at least one of the metal components remaining at least partially in the solid state during said process.

13.

The process of any one of claims 10-12 wherein, if a precursor of the combustible binder is present, the precursor becomes a combustible binder after the addition.

14.

The process of claim 13, wherein the precursor of the fuel binder is converted into the fuel binder by pyrolysis in an inert atmosphere at a temperature in the range of 300 ° -600 ° C.

fifteen.

The process of any one of claims 10-14, wherein the fuel binder or the fuel binder precursor is added in a liquid form, preferably in the form of a solution.

16. The process of any one of claims 10-15 further comprising a sulfurization step.

17.

Use of the catalyst composition of any of claims 1-9 for the hydroprocessing of hydrocarbon feedstocks.

18.

A process for recycling a catalyst according to any one of claims 1-9,

10 said process comprising thermally treating the catalyst composition in an oxygen-containing atmosphere at a temperature of at least 300 ° C.